Tricyclohexylphosphine complexes iridium

Tricyclohexylphosphine Complexes of Ruthenium, Rhodium, and Iridium and Their Reactivity Toward Gas Molecules... 

The complex has enjoyed relatively little use in organic synthesis. For iridium-catalyzed homogeneous hydrogenation of alkenes, Crabtree s iridium complex ((1,5-Cycloocta-diene)(tricyclohexylphosphine)(pyridine)iridium(I) Hexafluoro-phosphate) is generally preferred, although this readily prepared Ir complex is active. It is more reactive than its rhodium counterpart in the catalytic isomerization of butenyl- to allylsilanes. ... 

Tricyclohexylphosphine was obtained from Strem Chemicals. Ruthenium, rhodium, and iridium trichlorides were obtained as trihydrates from Johnson, Matthey Limited. Iridium tetrachloride was obtained from Platinum Chemicals. The precursor complexes [RhCl(COD)]2 (57), [RhCl(COT)2]2 (58), [RhCl(C2H4)2]2 (59), [IrCl(COD)]2 (14), and [HIrCl2-(COD)]2 (31) were made according to the literature procedures. 

Carbon ylchlorodihydridobis(tricyclohexylphosphine) iridium-(III), H2IrCl(CO)(PCy3)2, Complex 10. This complex was prepared from Complex 7 by the same procedure that 5 was prepared from 3. We found carbon, 54.6 hydrogen, 8.3. C37H6aOClP2Ir requires carbon, 54.3 hydrogen, 8.4. 

The olefin complexes of iron, nickel, rhodium, and iridium described in this chapter have found broad application in the synthesis of phosphine, phosphite, and carbonyl derivatives of these metals. In Chapter Two, the synthesis of another labile olefin complex, (ethylene)bis(tricyclohexylphosphine)nickel, is described as an initial step in synthesis of a complex of dinitrogen. 

OHj, Water, chromium and vanadium complexes, 27 307, 309 iridium complex, 26 123, 28 58 ruthenium complex, 26 254-256 OlPjRhCjjHgg, Rhodium(I), carbonyliodo-bis(tricyclohexylphosphine)-, 27 292 OLiNC,jH22, Lithium, (diethyl ether)(8-(dimethylamino)-l-naphthyll-, 26 154 OLUC21H25, Lutetium, bis(ii -Cyclopenta-dienyl)(tetrahydrofuran)-p-tolyl-,... 

Complexes of the type [Ir(bzn)(cod)(L)](C104) (bzn = benzonitrile L = tricyclohexylphosphine, neomenthyldiphenylphosphine) catalyze the homogeneous hydrogenation of tetrasubstituted prochiral amido alkenes R R C=CR N. Under very mild conditions, the catalysis occurs for N = NHCOR, R = COjMe R = R = Me, R" = Me, Ph R = Me, R- = Ph, R = Me, Ph R = Ph, R = Me, R = Ph. [Ir(cod)(PCy3)(py)](PFg) serves as a catalyst in the hydroxyl-directed hydrogenation of cyclic and acyclic alkenic alcohols, wherein the reaction shows diastereoselectivity dependent on catalyst substrate stoichiometry. Park el have noted that the iridium(I)... 

Examples of palladium- and rhodium-catalyzed hydroaminations of alkynes are shown in Equations 16.90-16.92 and Table 16.9. The reaction in Equation 16.90 is one of many examples of intramolecular hydroaminations to form indoles that are catalyzed by palladium complexes. The reaction in Equation 16.91 shows earlier versions of this transformation to form pyrroles by the intramolecular hydroamination of amino-substituted propargyl alcohols. More recently, intramolecular hydroaminations of alkynes catalyzed by complexes of rhodium and iridium containing nitrogen donor ligands have been reported, and intermolecular hydroaminations of terminal alkynes at room temperature catalyzed by the combination of a cationic rhodium precursor and tricyclohexylphosphine are known. The latter reaction forms the Markovnikov addition product, as shown in Equation 16.92 and Table 16.9. These reactions catalyzed by rhodium and iridium complexes are presumed to occur by nucleophilic attack on a coordinated alkyne. 

---